Bis[9-(2-cyanoalkyl) fluoren-9-yl] alkane compound



United States Patent This invention relates to novel fluorenederivatives. More particularly, this invention relates tobi1s[9(substituted alkyl)fluoren-9-yl]alkanes of the formula:

ZCHRCHg C Hz CHzCHRZ wherein n is an integer having a valve of from 2 to10 and preferably from 2 to 6; Z is a cyano radical, a -COOR radical, ora CI-I NHR radical; R is a hydrogen atom or a methyl radical; R is ahydrogen atom, an alkali metal atom, or an alkyl radical having from 1to about 10 carbon atoms; and R is a hydrogen atom or an alkanoylradical having from 1 to about carbon atoms in the alkyl radicalthereof. Thus, the compounds of this invention are novelbis[9-(2-cyanoalkyl)fiuoren-9- yl] alkanes; bis[9 (2carboxyalkyl)fluoren-9-yl] alkanes and their alkali metal salts or alkylesters; bis[9-(N-alkanoyl-3-aminoalkyl)fiuoren-9-yl] alkanes; and bis[9(3 aminoalkyl fiuoren-9-yl] alkanes.

The novel carboxyl and amino compounds of this invention are useful inthemselves as monomers for the formation of new polymers, such aspolyesters, polyamides, and the like; while the cyano compounds areuseful as intermediates for the production of polymerizable monomers.For example, the cyano derivatives of this invention can be hydrolyzedto form dicarboxylic acids which are useful in the production ofpolyesters or polyamides. The cyano derivatives can also be hydrogenatedin the presence of an alkali metal alkanoate to produce N- alkanoylaminoderivatives which can be hydrolyzed to form an amine derivative usefulin the production of polyamides, polyureas, and the like.

The novel bis[9-(substituted alkyl)fluoren-9-yl] alkanes of thisinvention are all readily produced from the bis(9- fluorenyl)alkanes ofthe formula:

wherein n is as previously defined. The bis(9-fiuorenyl) alkanes areproduced by reacting a fluorene with a diol in the presence of an alkalimetal hydroxide as a catalyst.

By the term fiuorene is meant both fiuorene and fluorene compounds whichare substituted on the aromatic rings with alkyl, aryl, alkaryl,aralkyl, alkoxy, aryloxy, alkaryloxy, and aralkoxy radicals having up tocarbon toms. As examples of suitable fiuorene compounds, one can mentionfiuorene, l-methylfiuorene, Z-methylfluorene, 3-methylfiuorene,4-methylfluorene, 5-methylfiuorene, 6-methylfiuorene, 7-methylfiuorene,8-methylfluorene, 2-hexylfiuorene, 2-phenylfluorene, 2-(1-naphthyl)fluorene, Z-(Z-methylphenyl)fluorene, Z-benzylfiuorene, 2methoxyfiuorene, 2 phenoxyfluorene, 2 (2 methylphenoxy)fluorene,2-benzyloxyfiuorene, and the like.

The diols employed to produce the bis(9-fluorenyl)alkanes arerepresented by the formula HOC H fir a wherein n is as defined above. Asexamples of suitable diols one can mention ethylene glycol, propyleneglycol, tetramethylene diol, decarnethylene diol, pentamethylene diol,hexamethylene diol, and the like. In producing thebis(9-fluorenyl)alkanes the concentration of diol in the charge can varyfrom about 0.1 mole or less to about 10 moles or more, per mole offiuorene compound charged, with from about 0.5 to about 2.0 mole of diolper mole of fluorene compound being preferred.

As stated above, an alkali metal hydroxide, such as lithium hydroxide,sodium hydroxide, potassium hydroxide, and the like, is employed as acatalyst in producing the bis(9-fluorenyl)alkanes, with potassiumhydroxide being preferred. The amount of alkali metal hydroxide used canvary from about 0.1 mole or less to about 1.0 mole or more per mole offluorene compound charged, with from about 0.2 to about 0.5 mole ofalkali metal hydroxide per mole of fiuorene compound being preferred.The reaction of diol with fiuorene is conducted at a temperature of fromabout C. or lower to about 275 C. or higher, with temperatures of fromabout 220 C. to about 250 C. being preferred.

The bis(9-fiuorenyl)alkane is readily recovered from the reactionmixture by slurrying the reaction mixture with water to dissolveunreacted diol and the alkali metal hydroxide and then filtering theinsoluble bis(9- fiuorenyl)alkane from the aqueous slurry. If desired,the bis(9-fiuorenyl)alkane can be further purified by washing with Wateror methanol, or by recrystallization from an organic solvent, forexample, 1,4-dioxane.

Reaction of the bis(9-fiuorenyl)alkane with a cyanoalkene such asacrylonitrile or methacrylonitrile produces thebis[9-(2-cyanoalkyl)fluoren-9-yl]alkanes having the formula:

Noonncfii onus. CHZCHRCN wherein n and R are as previously defined. Asexamples of these compounds one can mention1,2-bis[9-(2-cyanoethyl)fluoren 9-yl] ethane, 1,4-bis[9-(2-cyanoethyl)fiuoren 9-yl]butane,1,10-bis[9-(2-cyanoethyl)fiuoren-9-yl] decane,1,2-bis[9-(2-cyanopropyl)fluoren-9-yl]ethane, 1,IO-bi-s{9-(2-cyanopropyl)fiuoren 9 ylJdecane, and the like.

As indicated, the bis[9-(2-cyanoalkyl)fiuoren-9-yl] alkanes are producedby the cyanoalkylation of a bis(9- fiuorenyl)alkane with a cyanoalkenesuch as acrylonitrile or methacrylonitrile. The cyanoalkylation can becarried out at from about 10 C. to about 50 C., preferably from about 20C. to about 35 C., in the presence of a solvent for thebis(9-fiuorenyl)alkane, for example, benzene, dioxane, pyridine,acetonitrile, tert-butyl alcohol, etc. The mole ratio of cyanoalkene tobis(9-fluorenyl)alkane can vary from about 0.5 :1 or less to about 5:1or more, with ratios of from about 2:1 to about 3:1 preferred. Thecyanoalkylation is assisted by a basic catalyst, such as the oxides,hydroxides, alkoxides, hydn'des, cyanides, or amides of sodium orpotassium. Quaternary ammonium hydroxides such asbenzyltrimethylammonium hydroxide are particularly preferred ascatalysts. In general, the basic catalysts are employed in thecyanoalkylation reaction in an amount varying from about 0.5 to about 10weight percent, based upon the cyanoalkene, with from about 1 to about 5weight percent preferred. Although the reactants can be charged in anyorder, it is preferred to gradually add the cyanoalkene to a stirredmixture of catalyst, bis(9-fiuorenyl)alkane and solvent.

The bis[9-(Z-cyanoalkyl)fluoren-9-yl] alkanes are solids which can berecovered from the reaction mixture by filtration. Additionalbis[9-(Z-cyanoalkyl)fiuoren-9-yl] alkane can be recovered from thefiltrate by admixing the filtrate with water, whereupon thebi's[9-(2-cyano alkyl)fluoren-9-yl] alkane dissolved in the filtrateprecipitates out and can be recovered by filtration. The bis [9-(2-cyanoalkyl)fluoren-9-yl]alkane can then be purified by conventionalprocedures.

The bis[9-(2-carboxyalkyl)fluoren-9-yl]alkanes and the alkali metalsalts and alkyl esters thereof of this invention have the formula:

R OOOOHRCIL C Hg CH CI-IRCOOR wherein n, R and R =are as defined above.

As examples of the novel dicarboxylic acids one can mention 1,2-bis [9-(Z-carb oxyethyl fiuoren-9-yl] ethane, 1, 4-bis [9- Z-carboxyethylfiuoren-9-yl] -butane, l ,10-bis [9- (Z-carboxyethyl fluoren-9-yl]decane, 1,2-bis [9- 2-carboxypropyl)fiuoren 9-yl]e'thane,1,10-bis[9-(2-carboxypropyl)fiuoren-9-y1]decane, and the like. Thesedicarboxyic acid compounds are readily produced by the hydrolysis of thecorresponding bis[9-(Z-cyanoalkyl)fluoren-9-yl]alkane compound or by thereaction of an alkali metal acrylate or alkali metal methacrylate with abis(9-fiuorenyl)alkane followed by acidification of the resutingdialkali metal salt.

The hydrolysis of the bis[9-(2-cyanoalkyl)fiu0ren-9-yl] alkane to formthe bis[9-(Z-carboxyalkyl)uuoren-9-yl] alkane can be conducted bymethods known to those skilled in the art for the hydrolysis of thenitrile group. It is preferred, however, to reflux thebis[9-(2-cyanoalkyl) fiuoren-9-yl] alkane in admixture with water,acetic acid, and hydrobromic acid, there being at least four moles ofWater and at least two moles of hydrobromic acid per mole ofbis[9-(Z-cyanoalkyl)fiuoren-9-yl]alkane in the charge.

As indicated above, the bis[9-(2-carboxyalkyl)fluoren- 9-yl]alkane alsocan be produced by reacting an alkali metal acrylate or alkali metalmethacrylate with a bis(9- flu-orenyl)alkane in the presence of analkali metal hydroride as a catalyst. The mole ratio of alkali metalacrylate or alkali metal methacrylate to bis(9-fluorenyl) alka-ne in thecharge can vary from about 1:1 to about :1, with a mole ratio of fromabout 2:1 to about 3 :1 referred. The alkali metal hydroxide is employedin an amount varying from about 0.1 to about 5 weight percent, basedupon alkali metal acrylate or alkali metal methacrylate, with :fromabout 0.5 to about 3 weight percent preferred. The reaction is conductedat a temperature of from about 150 C. to about 350 C., with atemperature of from about 190 C. to about 290 C. preferred. Theimmediate products of this process are the dialkali metal salts of the(bis[9-(Z-carboxyalkyl)fiuoren-9-yl]alkanes such as the lithium, sodium,potassium, rubidium or cesium salts. These dialkali metal salts arereadily acidified by methods known to those skilled in the art toproduce the corresponding bis[9-(Z-carboxyalkyl)fluorene-9-yl] alkane.

The bis[9-(Z-ca-rboxyalkyl)fluoren-9-yl]alkanes are water-insolublesolids. Thus, they can be isolated from the reaction mixture from eitherof the foregoing processes by the addition of water and filtration ofthe aqueous miX- ture.

The bis[9-(2-carboxyalkyl)fiuoren-9-yl1alkanes readily converted totheir alkyl esters, of the formula:

IUOOCCHRCH; CnHZn CHzCHRCOOIH are procedures known to those skilled inthe art, such as refluxing the selected acid and alcohol in the presenceof an acid catalyst, for example, p-toluene sulfonic acid, to producethe ester, which is recovered by conventional procedures.

The bis[9 (N-alkanoyl-3-aminoalkyl)fluoren-9-yl] alkanes of thisinvention have the formula:

0 i \Q 0 ll I a cnncngcnaon, 0.11 bnzcnnomunh 11 wherein n and R are aspreviously defined and R is an alkyl radical of from 1 to 5 carbonatoms. As examples of these compounds one can mention1,2-bis[9-(N-acetyl- 3-aminopropyl)fluoren-9-yl]ethane,1,4-bis[9-(N-acetyl-3- aminopropyl)fluoren-9-yl] butane, 1,10-bis[9-(N-acetyl-3- aminopropyl )fluoren-9-yl] ethan, 1,2-bis [9-N-valeryl-3 aminopropyl) fluoren-9-yl] ethane, 1,2-bis [9- (N-acetyl-3-amino-Z-methylpropyl)fiuoren-9-yl]ethane, and the like.

The bis[9 (N-alkanoyl-3-aminoalkyl)tluoren-9-yl]alkanes or" thisinvention are produced, for example, by hydrogenation of a mixture of ahis [9-(2-cyanoalkyl)fiuoren 9-yl]a1kane, an alkanoic acid anhydride andan alkali metal alkanoate in contact with hydrogenation catalyst.

The alkanoic acid anhydrides suitable for use in producing thebis[9-(N-alkanoyl-3-arninoalkyl)fluoren-9- yl] alkanes of this inventionare the anhydrides of lower alkanoic acids such as acetic acid,propionic acid, butyric acid, pentanoic acid, and the like. In thisreaction, the mole ratio of acid anhydride to bis[9-(2-cyanoalkyl)fluoren-9-yl1alkane can vary from about 0.521 or less to about 4:1 orhigher, with mole ratios of from about 1:1 to about 2:1 preferred.

The alkali metal alkanoate employed is preferably the alkali metal saltof the alkanoic acid whose anhydride is employed during thehydrogenation reaction. The alkali metal salts can be the lithium,sodium, potassium, rubidium, or cesium salts of the alkanoic acid. Asexamples of suitable alkali metal alkanoates one can mention lithiumacetate, sodium acetate, potassium acetate, rubidium acetate, cesiumacetate, sodium propionate, sodium butyrate, sodium valerate, and thelike. In general, the alkali metal alkanoates are present in thereaction mixture in an amount varying from 5 to weight percent based onthe bis[9-(2-cyanoa1kyl)fluoren- 9-yl]alkane, with from 10 to 30 weightpercent preferred.

The hydrogenation catalyst can be any of the Raney metal catalysts knownto the art, with Raney nickel being preferred. The catalyst is employedin amounts varying from 2 to 40 weight percent, based on the bis[9-(2-'cyanoalkyl)fluoren-9-yl] alkane, with amounts of from 10 an dHgNCHzCHROH C Hgn CH OHRCHgNHg wherein n and R are as previouslydefined. As examples of these novel diamines one can mention1,2-bis[9-(3- aminopropyl)fiuoren-9-yl]ethane, 1,4-bis[9-(3-aminopropylfiuoren-9-yl] butane, 1,10-bis [9-(3-aminopr0pyl)fluoren-9-yl1decane,1,2 bis[9-(3-amino 2-methylpropyl) fiuoren-9-yl1ethane, and the like.

The bis[9-(3-aminoalkyl)fluoren-9-yl]alkanes of this invention arereadily produced by hydrolysis of the bis[9-(N-alkanoyl-3-aminoalkyl)fluoren-9-yl] alkanes of the invention. Thehydrolysis can be accomplished by methods known to those skilled in theart, such as by heating in contact with a mixture of aqueous sodiumhydroxide and methanol at a temperature of from about 150 C. to 250 C.

Ths bis[9-(3-aminoalkyl)fluoren-9-yl]alkanes can also be produced byreduction of the bis[9-(2-cyanoalkyl) fluoren-9-yl1a1kanes of thisinvention, such as by the lithium aluminum hydride reduction of thebis[9-(2- cyanoalkyl) fiuoren-9-yl] alkanes.

The following examples are illustrative:

EXAMPLE I 1 ,2-bis (9-flu0renyl) ethane A three-liter rocker autoclavewas charged with 332 grams of fluorene, 500 grams of ethylene glycol,and 85 grams of potassium hydroxide. The autoclave was sealed, pressuredto 25 p.s.i.g. with air and heated at 220 C. for 20 hours whileagitating by rocking. The autoclave was cooled, opened and the contentswere removed and slurried in 1 liter of water. After filtration from theaqueous slurry, washing with water and then with methanol and drying,the 1,2bis(9-fluorenyl)ethane produced weighed 157 grams and melted at228-229.5 C.

EXAMPLE II 1,6-bis(9-fluorenyl) hexane Employing apparatus andprocedures similar to those disclosed in Example I, 166 grams offluorene, 70 grams of 1,6-hexanediol and 42.5 grams of potassiumhydroxide were reacted at 210-220 C. for 4 hours to produce 143 grams of1,6-bis(9-fluorenyl)hexane. After recrystallizing from a mixture ofisopropanol and dioxane the 1,6- bis(9-fluorenyl)hexane melted at109l09.5 C.

EXAMPLE III 1,2-bis[9- (Z-cyanoethyl) fluoren-Q-jyl] ethane To a chargecontaining 36 grams of 1,2-bis(9-fluorenyl) ethane, 750 cc. of dioxaneand 10 cc. of a 32 percent solution of benzyltrimethylammonium hydroxidein methanol as a catalyst, there were slowly added 20 grams ofacrylonitrile with stirring. The temperature of the reaction mixturerose from 27 C. to 37 C. After cooling to 29 C. and stirring for another2 hours, an additional 10 cc. of the benzyltrimethylamrnoniumhydroxidemethanol solution and 20 grams of acrylonitrile were added. Thereaction mixture was filtered and the solid 1,2-bis[9-(Z-cyanoethyl)fluoren-9-yl]ethane was recovered, which, afterrecrystallization from dioxane, weighed 26 grams and melted at 275277 C.

Micr0analysis.Calculated for C H N C, 89.94%; H, 6.03%; N, 6.03%. Found:C, 89.95%; H, 6.10%; N, 6.20%

The structure of the 1,2-bis[9-(2-cyanoethyl)fluoren- 9-yl]ethane wasfurther confirmed by infrared spectroscopy.

In a similar manner, 1,2-bis[9-(2-cyanopropyl)fiuoren- 9-yl]ethane isproduced by substituting methacrylonitrile for acrylonitrile.

EXAMPLE IV Employing apparatus and procedures similar to those describedin Example III, 40 grams of 1,4-bis(9-fluorenyl) butane (produced in amanner similar to that described in Example I by reacting fluorene with1,4-butane diol in the presence of potassium hydroxide) were reactedwith 16 grams of acrylonitrile to produce 34 grams of 1,4-bis[9-(2-cyanoethyl)fiuoren-9-yl]butane which, after recrystallizationfrom an isopropanol-benzene mixture, melted at 181 C.182 C.

6 Microanalysis.Calculated for C H N C, 87.78%; H, 6.54%; N, 5.68%.Found: C, 87.73%; H, 6.78%; N, 5.89%.

EXAMPLE V 1 ,5 -bis [9- Z-cyanoethyl flu0ren-9-yl pentane Employingapparatus and procedures similar to those described in Example III, 30grams of 1,5-bis(9-fiuorenyl) pentane (produced in a manner similar tothat described in Example I by reacting fluorene with 1,5-pentane diolin the presence of potassium hydroxide) were reacted with 16 grams ofacrylonitrile to produce 26 grams of 1,5-bis[9-(2-cyanoethyl)fluoren-9-yl] pentane which, after recrystallizationfrom methanol, melted at -121 C.

Micr0analysis.Calculated for C H N C, 87.61%; H, 6.76%; N, 5.53%. Found:C, 88.01%; H, 6.69%; N, 5.65%.

EXAMPLE VI Employing apparatus and procedures similar to those describedin Example III, 34 grams of 1,6-bis(9-fluorenyl) hexane were reactedwith 16 grams of acrylonitrile to produce 31 grams of 1,6-bis9-(2-cyanoethyl)fiuoren-9- yl]hexane which, after recrystallization frommethanol, melted at l25.5126.5 C.

Microanalysis.Calculated for C H N C, 87.66%; H, 6.96%; N, 5.38%. Found:C, 87.38%; H, 6.90%; N, 5.57%.

EXAMPLE VII 1,2-bis [9- (Z-carboxyethyl)fluoren-Q-yl] ethane A mixtureof 300 grams of 1,2-bis[9-(2-cyanoethyl) fluoren-9-yl]ethane, 750 gramsof acetic acid and 750 grams of aqueous 48 percent hydrobromic acid ascatalyst was refluxed vigorously for 4 days. After filtration from thereaction mixture, Washing with water and recrystallization from dioxane,there were obtained 277 grams of 1,2-bis[9-(2 carboxyethyl)fluoren 9yl]ethane which melted at 285-287 C.

Microanalysis.Calculated for C H O C, 81.27% H, 5.98%. Found: C, 81.02%;H, 6.09%.

The structure of the 1,2-bis[9-(2-carboxyethyl)fiuoren- 9-yl]ethane wasfurther confirmed by infrared spectroscopy.

In a similar manner, fluoren-9-yl]ethane is produced by substituting,1,2-bis [9-(2-cyanopropyl)fiuoren-9-yl]ethane for 1,2-bis[9-(2-cyanoethyl) fluoren-9-yl] ethane.

Employing apparatus and procedures similar to those described in ExampleVII, 10 grams of 1,4-bis[9-(2- cyanoethyl)fluoren-9-yl]butane, 200milliliters of acetic acid and 200 milliliters of aqueous 48 percenthydrobromic acid were refluxed for 16 hours to produce 8 grams of1,4-bis[9-(2-carboxyethyl)fluoren-9-yl] butane which, afterrecrystallization from isopropanol, melted at 261- 263 C.

Micr0analysis.-Calculated for C H O C, 81.48%; H, 6.45%. Found: C,81.49%; H, 6.51%.

Employing apparatus and procedures similar to those described in ExampleVII, 10 grams of l,5-bis[9-(2-cyanoethyl)fiuoren-*9-yl]pentane, 200milliliters of acetic acid and 200 milliliters of aqueous 48 percenthydrobromic acid were refluxed for 16 hours to produce 10 grams of1,S-bis[9-(2-carboxyethyl)fiuoren 9 yl]pentane which, afterrecrystallization from a cyclohexane-benzene-isopropanol mixture, meltedat 180-181" C.

Micr0analysis.Calculated for C H O C, 81.58%; H, 6.66%. Found: C,81.34%; H, 6.69%.

1-2-bis[9-(2-carboxypropyl) I 7 EXAMPLE X 1 ,6-bis[9- (Z-carboxyethylfluoren-Q-yl] hexane Employing apparatus and procedures similar to thosedescribed in Example VII, 10 grams of 1,6-bis[9-(2-cyanoethyl)fluoren-9-yl1hexane, 200-milliliters of acetic acid,and 200 milliliters of aqueous 48 percent hydrobromic acid were refluxedfor 16 hours to produce 10 grams of 1,6-bis[9-(2-carboxyethyl)fluoren 9yl]hexane which, after recrystallization from isopropanol, melted at218- 219 C.

Micraanalysz's.-Calculated for C H O C, 81.69%; H, 6.86%. Found: C,81.75%; H, 7.11%.

EXAMPLE XI 1,2-bis [9- (2-carb0xyethyl)fluoren-Q-yl] ethane1,2-bis[9-(2-carboxyethyl)fluoren-9-yl]ethane is produced by reacting1,2-bis(9-fiuorenyl)ethane with potassium acrylate in the presence ofpotassium hydroxide at about 300 C. to produce the dipotassium salt of1,2- bis[9-(Z-carboxyethyl)fluoren-9-yl]ethane and acidifying thereaction mixture with aqueous hydrochloric acid to liberate the freeacid.

In a similar manner, 1,2-bis[9-(2-carboxypropyl)fiuoren-9-yl1ethane isproduced by substituting potassium methacrylate for potassium acrylate.

EXAMPLE XII 1,6-bis [9- (N-acezyl-3-amin0propyl) fluoren-Q-yl] hexane Ahydrogenating vessel was charged with 10 grams of1,6-bis[9-(2-cyanoethyl)fiuoren-9-yl1hexane, 100 grams of aceticanhydride, 2 grams of sodium acetate and about 3 grams of neutral Raneynickel catalyst. The hydrogenerator was sealed, pressured to 59.5p.s.i.g. with hydrogen and heated at 80 C. for 6 hours, over which timethe hydrogen pressure decreased to 52 p.s.i.g. The hydrogenerator Wascooled, opened, and the contents were fil tered to remove the Raneynickel. The filtrate was added to 500 milliliters of water, whereuponthe 1,6-bis[9-(N- acetyl-3-aminopropyl)fiuoren=9-yl]hexane producedprecipitated. After filtration and recrystallization from hex.-ane-isopropanol mixture, it weighed 10 grams and melted at 176179 C.After two additional recrystallizations from a hexane-isopropanolmixture the 1,6-bis[9-(N-acetyl-3-aminopropyl)fiuoren-9-yl]hexane meltedat 177- 180 C.

Micranalysis.-Calculated for C H ON C, 82.4%; H, 7.9%; N, 4.6%. Found:C, 82.4%; H, 8.0%; N, 4.2%.

EXAMPLE XIII 1 ,2-bis[ 9- N -acety l-3-amin0 propyl fluoren-Q-yl ethaneEmploying apparatus and procedures similar to those described in ExampleXII, 10 grams of 1,2-bis[9-(2-cyanoethyl)fiuoren-9-y1] ethane, 100 gramsof acetic anhydride, 2 grams of sodium acetate and about 3 grams ofRaney nickel catalyst were hydrogenated at 3545 C. for 5 hours toproduce 9 grams of1,2-bis[9-(N-acetyl-3-aininopropyl)fluoren-9-yl1ethane, which, afterrecrystallization from dioxane, melted at 267.5-269.5 C.

Microanalysis.-Calculated for C H N O C, 82.0% H, 7.2%; N, 5.0%. Found:C, 81.8%; H, 7.1%; N, 4.7%.

' In a similar manner 1,2-bis[9-(N-acetyl3-amino-2-methylpropyl)fluoren-9-yl]ethane is produced by substituting1,2-bis[9-(Z-cyanopropyl)fluoren-9-yl1ethane for 1 ,2-bis [9-(2-cyanoethyl)fluoren-9-yl] ethane, and 1,2-bis(N-valeryl-3-aminopropyl)fluoren-9-yl] ethane is produced bysubstituting valeric anhydride for acetic anhydride and sodium valeratefor sodium acetate.

EXAMPLE XIV 1 ,Z-bis [9- (3 -amz'nopr0pyl fluoren-Q-yl ethane A rockerautoclave was charged with 10 grams of 1,2- bis[9 (N-acetyl 3aminopropyl)fluoren-9-yl1ethane, 8 grams of sodium hydroxide, 10 gramsof water and 200 milliliters of methanol. The autoclave was sealed andheated at 196205 C. for 10 hours while agitating the reaction mixture byrocking. The autoclave was cooled, opened and the contents were pouredinto 750 milliliters of water, whereupon1,2-bis[9-(3-aminopropyl)fiuoren-9- yIJethane precipitated, which, afterfiltering and drying, weighed 6 grams. After recrystallization fromcyclohexane the 1,2-bis[9-(3-aminopropyl)fiuoren 9 yl]ethane melted at208210 C.

Micronnalysis.-Calculated for C H N C, 86.4%; H, 7.7%; N, 5.9%. Found:C, 86.0%; H, 7.5%; N, 6.0%.

The structure of the 1,2-bis[9-(3-aminopropyl)fiuoren- 9-yl]ethane wasfurther confirmed by infrared spectroscopy.

In a similar manner, 1,Z-bis[9*(3-amino-2-methylpropyl)fiuoren-9-yl]ethane is produced by substituting 1,2- bis[9-(N-acetyl3-amino 2methylpropyl)fiuoren-9-yl] ethane for1,2-bis[-9-(N-acetyl-3-aminopropyl)fluoren-9 yl]ethane.

What is claimed is:

1. A bis-[9-(Z-cyanoalkyl)fiuoren-9-yl]alkane of the formula wherein nis an integer having a value of from 2 to 10 and R is a member selectedfrom the group consisting of hydrogen and methyl.

2. 1,2-bis [9- (Z-cyanoethyl fiuoren-9-yl] ethane.

3. 1,4-bis 9- Z-cyanoethyl fluoren-9-yl] butane.

4. 1,5 -bis [9- Z-cyanoethyl fiuoren-9-yl] pentane.

5. 1,6-bis [9- (Z-cyanoethyl fluoren-9-yl] hexane.

References Cited by the Examiner UNITED STATES PATENTS 1,836,940 12/31Sibley 260-5708 2,195,289 3/40 Sheldrick et al 260-558 2,516,098 7/50Bambas 260-562 2,546,762 3/51 Long 260-562 2,572,510 -10/51 Allen et al260-4655 2,590,079 3/52 Abel et al 260-5708 2,656,388 10/53 Schultz260-5708 2,779,780 1/ 57 Middleton 260-4665 2,969,389 1/61 Kundiger eta1. 260-515 2,971,980 2/61 Tinsley 260-515 CHARLES B. PARKER, PrimaryExaminer.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 ,205257 September 7 1965 Henry E. Fritz et al.

It is hereby certified that error appears in the above numbered patentrequiring correction and that the said Letters Patent should read ascorrected below.

Column 1, line 70 for "HOC H q) read HOC H OH column 3, line 30, for"bis[9(2carboxyalkyl)uuoren-Q-yl]" readbis[9-(2-carboxyalkyl)fluoren-Q-yl] column 4, line 19, for"aminopropyljfluoren-Q-yl]ethan" read aminopropyl)fluoren-9-yl]decanecolumn 5, line 49, for "hydroxidemeth-" read hydroxide-methcolumn 6,line 24, for "l ,6-bis 9 (2-cyanoethyl) f1uoren-9" read 1 ,6-bis [9- (2-cyanoethyl)fluoren-9 line 74, for "6 11 0 read (1 N 0 column 7, line 48,for "C H ON read 42 48 2 Z Signed and sealed this 10th day of May 1966.

(SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner ofPatents

1. A BIS-(9-(2-CYANOALKYL)FLUOREN-9-YL)ALKANE OF THE FORMULA: